Curable polymeric materials and their use for fabricating electronic devices

ABSTRACT

The present teachings relate to curable linear polymers that can be used as active and/or passive organic materials in various electronic, optical, and optoelectronic devices. In some embodiments, the device can include an organic semiconductor layer and a dielectric layer prepared from such curable linear polymers. In some embodiments, the device can include a passivation layer prepared from the linear polymers described herein. The present linear polymers can be solution-processed, then cured thermally (particularly, at relatively low temperatures) and/or photochemically into various thin film materials with desirable properties.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of U.S. ProvisionalPatent Application Ser. No. 62/192,055 filed on Jul. 13, 2015, thedisclosure of which is incorporated by reference herein in its entirety.

INTRODUCTION

In the past decade, there has been a growing interest in developingelectronic devices using organic or amorphous materials as thesemiconductor component. These devices can offer advantages such asstructural flexibility, potentially much lower manufacturing costs, andthe possibility of low-temperature ambient manufacturing processes onlarge areas. For example, both organic and amorphous materials can beused to enable new devices such as electronic paper, flexible organiclight-emitting diodes (OLEDs), and radio-frequency identification (RFID)technologies.

One of the key benefits to using organic and amorphous materials is thepotential to use solution-phase deposition techniques, although thelatter also can be deposited using various vapor-phase approaches. Yet,to fully realize the processing advantages of organic or amorphoussemiconductors, all active components of the device should bemechanically flexible and preferably, most of the components of thedevice should be compatible with, if not processable by, solution-phasedeposition fabrication.

For example, thin-film transistors (TFTs) based upon varioussolution-processed organic semiconductors as well as solution-processedor vapor-deposited metal oxide semiconductors have been developed.However, a critical component in TFTs is the dielectric layer, whichserves as the gate electrical insulator material. In addition toexhibiting low-gate leakage properties, a good dielectric material alsoneed to be air and moisture-stable, and should be robust enough towithstand various conditions that are common in device fabricationprocesses, with properties that are tunable depending on the type ofsemiconductor employed in the TFT channel. Furthermore, to enable arobust fabrication process and stable device operation, optimization ofthe multilayer TFT structure by using appropriate material combinationsis necessary. Thus, the substrate surface should be treated or coated tobe compatible with the overlying layers fabricated on top of it. Thesemiconductor (the layer within which charge transport occurs) needs tobe uniformly deposited. If the semiconductor is inorganic, amorphousmaterials usually are employed; and if the semiconductor is organic,additives typically are used in the formulation to facilitate coating.In addition, after the device is completed, a top layer often is used toprotect the TFT stack from the environment during operation.

Accordingly, there is a desire in the art to design and synthesize neworganic materials that are compatible with diverse substrates, metalliccontacts, and/or semiconductor materials such that they could beemployed in the whole TFT fabrication process to meet one or more devicerequirements including low current leakage densities, tuned surfaceenergies, good adhesion, good solution-processability, and/or lowpermeation to water.

SUMMARY

In light of the foregoing, the present teachings provide organicmaterials that possess one or more desirable properties andcharacteristics which make them suitable as active (e.g., dielectric)and/or passive (e.g., passivation or surface-modifying) materials in anelectronic device such as a field-effect transistor.

More specifically, the present organic materials are based upon a linearpolymer that can be deposited from a solution, then curable into aphysically robust and ambient-stable thin film. In various embodiments,the linear polymer can comprise a repeating unit of formula (A):

wherein:X and Y independently are selected from the group consisting of CH₂,CHR, CR₂, C(O), SiH₂, SiHR, SiR₂, NH, NR, O, and S, wherein

-   -   R is selected from the group consisting of a halogen, —OR^(a),        —C(O)OR^(a), —OC(O)R^(a), —NR^(b)R^(c), —C(O)NR^(b)R^(c),        —OC(O)NR^(b)R^(c), a C₁₋₁₀ alkyl group, a C₁₋₁₀ haloalkyl group,        and an optionally substituted aryl or heteroaryl group,    -   R^(a) is a C₁₋₁₀ alkyl group or a —Si(C₁₋₁₀ alkyl)₃ group, and    -   R^(b) and R^(c) independently are H or a C₁₋₁₀ alkyl group;        W—Z is CH═CH or

R¹, R², R³, and R⁴ independently are selected from the group consistingof H, —OR^(d), —C(O)OR^(d), —OC(O)R^(d), a C₁₋₁₀ alkyl group, a C₁₋₁₀haloalkyl group, and L-Q, wherein

-   -   L is selected from the group consisting of —O—, —C(O), a        divalent C₁₋₁₀ alkyl group, a divalent C₆₋₁₈ aryl group, a        covalent bond, and combinations thereof, Q is a crosslinkable        group comprising an ethenyl moiety, an ethynyl moiety, a dienyl        moiety, an acrylate moiety, a coumarinyl moiety, an epoxy        moiety, or a combination thereof, and    -   R^(d) is H or a C₁₋₁₀ alkyl group,        provided that at least one of R¹, R², R³, and R⁴ is L-Q; and        m is 0, 1 or 2.

The present teachings also provide organic materials comprising uncuredor cured films of the linear polymer described herein, compositions thatcan be used to prepare the organic materials using a solution-phaseprocess, as well as electronic devices that include the organicmaterials.

Methods for preparing the linear polymers, the organic materialscomprising the linear polymers, and electronic devices that incorporatethe organic materials also are provided and are within the scope of thepresent teachings.

The foregoing as well as other features and advantages of the presentteachings will be more fully understood from the following figures,description, and claims.

BRIEF DESCRIPTION OF DRAWINGS

It should be understood that the drawings described below are forillustration purpose only. The drawings are not necessarily to scale,with emphasis generally being placed upon illustrating the principles ofthe present teachings. The drawings are not intended to limit the scopeof the present teachings in any way.

FIG. 1 illustrates four different configurations of thin filmtransistors: a) bottom-gate top contact, b) bottom-gate bottom-contact,c) top-gate bottom-contact, and d) top-gate top-contact; each of whichcan be used to incorporate one or more linear polymers of the presentteachings as active and/or passive materials.

FIG. 2 shows a bottom-gate top-contact thin film transistor,illustrating that the linear polymers of the present teachings can beemployed as a surface modifying layer (layer 1), a gate dielectric layer(layer 2), an additive within the semiconductor layer (layer 3), and/oran etch-stop/blocking/passivation/barrier/encapsulation layer (layer 4).

FIG. 3 shows a representative transfer plot of a top-gate bottom-contactPDICN₂-based OTFT incorporating a dielectric layer according to thepresent teachings, where the dielectric layer has a thickness of about800 nm and is a linear poly(5-norbornene-2-methylcinnamate) that wascrosslinked under flood UV (1090 mJ) and cured for 10 minutes at 110° C.

DETAILED DESCRIPTION

The present teachings relate to organic materials that can be used asactive and/or passive materials in a wide variety of electronic,optical, and optoelectronic devices such as thin film transistors(TFTs), specifically, organic field-effect transistors (OFETs),semiconductor oxide field-effect transistor (SOFETs), as well assensors, capacitors, unipolar circuits, complementary circuits (e.g.,inverter circuits), and the like.

Generally, the present organic materials are prepared from a linearpolymer comprising a repeating unit that provides an unsaturated bond inthe polymer backbone and includes a crosslinkable pendant group. Such alinear polymer can be solution-processed into thin films, where the thinfilms subsequently can be cured (thermally and/or photochemically) intophysically robust and ambient-stable active or passive materialssuitable for use in various electronic, optical, and optoelectronicsdevices. For example, the organic materials according to the presentteachings can be used (either by itself or with at least one otherdielectric material) as the dielectric layer in a thin film transistor,as an etch-stop/blocking/passivation/encapsulation/barrier material (forexample, to encapsulate the source and drain electrodes in atransistor), as an interfacial material (for example, asurface-modifying interlayer), or as a component in the semiconductorlayer.

When used as a dielectric material, the present organic materials canexhibit a wide range of desirable properties and characteristicsincluding, but not limited to, low leakage current densities, highbreakdown voltages, low hysteresis, tuned capacitance values, uniformfilm thickness, solution-processability, fabricability at lowtemperatures and/or atmospheric pressures, air and moisture stability,and/or compatibility with diverse gate materials and/or semiconductors.When used as passivation or interfacial materials, the present organicmaterials can exhibit desirable properties and characteristicsincluding, but not limited to, high glass transition temperature, highoptical clarity, low shrinkage, low moisture absorption, low oxygenpenetration, uniform film thickness, solution-processability,fabricability at low temperatures and/or atmospheric pressures, and goodadhesion to adjacent materials.

Throughout the application, where compositions are described as having,including, or comprising specific components, or where processes aredescribed as having, including, or comprising specific process steps, itis contemplated that compositions of the present teachings also consistessentially of, or consist of, the recited components, and that theprocesses of the present teachings also consist essentially of, orconsist of, the recited process steps.

In the application, where an element or component is said to be includedin and/or selected from a list of recited elements or components, itshould be understood that the element or component can be any one of therecited elements or components or can be selected from a groupconsisting of two or more of the recited elements or components.Further, it should be understood that elements and/or features of acomposition, an apparatus, or a method described herein can be combinedin a variety of ways without departing from the spirit and scope of thepresent teachings, whether explicit or implicit herein.

The use of the terms “include,” “includes”, “including,” “have,” “has,”or “having” should be generally understood as open-ended andnon-limiting unless specifically stated otherwise.

The use of the singular herein includes the plural (and vice versa)unless specifically stated otherwise. In addition, where the use of theterm “about” is before a quantitative value, the present teachings alsoinclude the specific quantitative value itself, unless specificallystated otherwise. As used herein, the term “about” refers to a ±10%variation from the nominal value unless otherwise indicated or inferred.

It should be understood that the order of steps or order for performingcertain actions is immaterial so long as the present teachings remainoperable. Moreover, two or more steps or actions may be conductedsimultaneously.

As used herein, “halo” or “halogen” refers to fluoro, chloro, bromo, andiodo.

As used herein, “oxo” refers to a double-bonded oxygen (i.e., ═O).

As used herein, “alkyl” refers to a straight-chain or branched saturatedhydrocarbon group. Examples of alkyl groups include methyl (Me), ethyl(Et), propyl (e.g., n-propyl and iso-propyl), butyl (e.g., n-butyl,iso-butyl, sec-butyl, tert-butyl), pentyl groups (e.g., n-pentyl,iso-pentyl, neopentyl), hexyl groups, and the like. In variousembodiments, an alkyl group can have 1 to 40 carbon atoms (i.e., C₁₋₄₀alkyl group), for example, 1-20 carbon atoms (i.e., C₁₋₂₀ alkyl group).In some embodiments, an alkyl group can have 1 to 6 carbon atoms, andcan be referred to as a “lower alkyl group.” Examples of lower alkylgroups include methyl, ethyl, propyl (e.g., n-propyl and iso-propyl),butyl (e.g., n-butyl, iso-butyl, sec-butyl, tert-butyl), and hexylgroups. In some embodiments, alkyl groups can be substituted asdescribed herein. An alkyl group is generally not substituted withanother alkyl group, an alkenyl group, or an alkynyl group.

As used herein, “haloalkyl” refers to an alkyl group having one or morehalogen substituents. At various embodiments, a haloalkyl group can have1 to 40 carbon atoms (i.e., C₁₋₄₀ haloalkyl group), for example, 1 to 20carbon atoms (i.e., C₁₋₂₀ haloalkyl group). Examples of haloalkyl groupsinclude CF₃, C₂F₅, CHF₂, CH₂F, CCl₃, CHCl₂, CH₂Cl, C₂Cl₅, and the like.Perhaloalkyl groups, i.e., alkyl groups where all of the hydrogen atomsare replaced with halogen atoms (e.g., CF₃ and C₂F₅), are includedwithin the definition of “haloalkyl.” For example, a C₁₋₄₀ haloalkylgroup can have the formula —C_(z)H_(2z+1−t)X⁰ _(t), where X⁰, at eachoccurrence, is F, Cl, Br or I, z is an integer in the range of 1 to 40,and t is an integer in the range of 1 to 81, provided that t is lessthan or equal to 2z+1. Haloalkyl groups that are not perhaloalkyl groupscan be substituted as described herein.

As used herein, “alkoxy” refers to —O-alkyl group. Examples of alkoxygroups include, but are not limited to, methoxy, ethoxy, propoxy (e.g.,n-propoxy and isopropoxy), t-butoxy, pentoxyl, hexoxyl groups, and thelike. The alkyl group in the —O-alkyl group can be substituted asdescribed herein.

As used herein, “alkylthio” refers to an —S— alkyl group. Examples ofalkylthio groups include, but are not limited to, methylthio, ethylthio,propylthio (e.g., n-propylthio and isopropylthio), t-butylthio,pentylthio, hexylthio groups, and the like. The alkyl group in the—S-alkyl group can be substituted as described herein.

As used herein, “alkenyl” refers to a straight-chain or branched alkylgroup having one or more carbon-carbon double bonds. Examples of alkenylgroups include ethenyl, propenyl, butenyl, pentenyl, hexenyl,butadienyl, pentadienyl, hexadienyl groups, and the like. The one ormore carbon-carbon double bonds can be internal (such as in 2-butene) orterminal (such as in 1-butene). In various embodiments, an alkenyl groupcan have 2 to 40 carbon atoms (i.e., C₂₋₄₀ alkenyl group), for example,2 to 20 carbon atoms (i.e., C₂₋₂₀ alkenyl group). In some embodiments,alkenyl groups can be substituted as described herein. An alkenyl groupis generally not substituted with another alkenyl group, an alkyl group,or an alkynyl group.

As used herein, “alkynyl” refers to a straight-chain or branched alkylgroup having one or more triple carbon-carbon bonds. Examples of alkynylgroups include ethynyl, propynyl, butynyl, pentynyl, hexynyl, and thelike. The one or more triple carbon-carbon bonds can be internal (suchas in 2-butyne) or terminal (such as in 1-butyne). In variousembodiments, an alkynyl group can have 2 to 40 carbon atoms (i.e., C₂₋₄₀alkynyl group), for example, 2 to 20 carbon atoms (i.e., C₂₋₂₀ alkynylgroup). In some embodiments, alkynyl groups can be substituted asdescribed herein. An alkynyl group is generally not substituted withanother alkynyl group, an alkyl group, or an alkenyl group.

As used herein, “cyclic” refers to an organic closed-ring groupincluding cycloalkyl groups, aryl groups, cycloheteroalkyl groups, andheteroaryl groups as defined herein.

As used herein, “cycloalkyl” refers to a non-aromatic carbocyclic groupincluding cyclized alkyl, cyclized alkenyl, and cyclized alkynyl groups.In various embodiments, a cycloalkyl group can have 3 to 40 carbon atoms(i.e., C₃₋₄₀ cycloalkyl group), for example, 3 to 20 carbon atoms. Acycloalkyl group can be monocyclic (e.g., cyclohexyl) or polycyclic(e.g., containing fused, bridged, and/or spiro ring systems), where thecarbon atoms are located inside the ring system. Any suitable ringposition of the cycloalkyl group can be covalently linked to the definedchemical structure. Examples of cycloalkyl groups include cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl,cyclohexenyl, cyclohexadienyl, cycloheptatrienyl, norbornyl, norpinyl,norcaryl, adamantyl, and spiro[4.5]decanyl groups, as well as theirhomologs, isomers, and the like. In some embodiments, cycloalkyl groupscan be substituted as described herein.

As used herein, “heteroatom” refers to an atom of any element other thancarbon or hydrogen and includes, for example, nitrogen, oxygen, silicon,sulfur, phosphorus, and selenium.

As used herein, “cycloheteroalkyl” refers to a non-aromatic cycloalkylgroup that contains at least one ring heteroatom selected from O, S, Se,N, P, and Si (e.g., O, S, and N), and optionally contains one or moredouble or triple bonds. A cycloheteroalkyl group can have 3 to 40 ringatoms (i.e., 3-40 membered cycloheteroalkyl group), for example, 3 to 20ring atoms. One or more N, P, S, or Se atoms (e.g., N or S) in acycloheteroalkyl ring may be oxidized (e.g., morpholine N-oxide,thiomorpholine S-oxide, thiomorpholine S,S-dioxide). In someembodiments, nitrogen or phosphorus atoms of cycloheteroalkyl groups canbear a substituent, for example, a hydrogen atom, an alkyl group, orother substituents as described herein. Cycloheteroalkyl groups can alsocontain one or more oxo groups, such as oxopiperidyl, oxooxazolidyl,dioxo-(1H,3H)-pyrimidyl, oxo-2(1H)-pyridyl, and the like. Examples ofcycloheteroalkyl groups include, among others, morpholinyl,thiomorpholinyl, pyranyl, imidazolidinyl, imidazolinyl, oxazolidinyl,pyrazolidinyl, pyrazolinyl, pyrrolidinyl, pyrrolinyl, tetrahydrofuranyl,tetrahydrothiophenyl, piperidinyl, piperazinyl, and the like. In someembodiments, cycloheteroalkyl groups can be substituted as describedherein.

As used herein, “aryl” refers to an aromatic monocyclic hydrocarbon ringsystem or a polycyclic ring system in which two or more aromatichydrocarbon rings are fused (i.e., having a bond in common with)together or at least one aromatic monocyclic hydrocarbon ring is fusedto one or more cycloalkyl and/or cycloheteroalkyl rings. An aryl groupcan have 6 to 40 carbon atoms in its ring system, which can includemultiple fused rings. In some embodiments, a polycyclic aryl group canhave from 8 to 40 carbon atoms. Any suitable ring position of the arylgroup can be covalently linked to the defined chemical structure.Examples of aryl groups having only aromatic carbocyclic ring(s) includephenyl, 1-naphthyl (bicyclic), 2-naphthyl (bicyclic), anthracenyl(tricyclic), phenanthrenyl (tricyclic), and like groups. Examples ofpolycyclic ring systems in which at least one aromatic carbocyclic ringis fused to one or more cycloalkyl and/or cycloheteroalkyl ringsinclude, among others, benzo derivatives of cyclopentane (i.e., anindanyl group, which is a 5,6-bicyclic cycloalkyl/aromatic ring system),cyclohexane (i.e., a tetrahydronaphthyl group, which is a 6,6-bicycliccycloalkyl/aromatic ring system), imidazoline (i.e., a benzimidazolinylgroup, which is a 5,6-bicyclic cycloheteroalkyl/aromatic ring system),and pyran (i.e., a chromenyl group, which is a 6,6-bicycliccycloheteroalkyl/aromatic ring system). Other examples of aryl groupsinclude benzodioxanyl, benzodioxolyl, chromanyl, indolinyl groups, andthe like. In some embodiments, aryl groups can be substituted asdescribed herein. In some embodiments, an aryl group can have one ormore halogen substituents, and can be referred to as a “haloaryl” group.Perhaloaryl groups, i.e., aryl groups where all of the hydrogen atomsare replaced with halogen atoms (e.g., —C₆F₅), are included within thedefinition of “haloaryl.” In certain embodiments, an aryl group issubstituted with another aryl group and can be referred to as a biarylgroup. Each of the aryl groups in the biaryl group can be substituted asdisclosed herein.

As used herein, “heteroaryl” refers to an aromatic monocyclic ringsystem containing at least one ring heteroatom selected from oxygen (O),nitrogen (N), sulfur (S), silicon (Si), and selenium (Se) or apolycyclic ring system where at least one of the rings present in thering system is aromatic and contains at least one ring heteroatom.Polycyclic heteroaryl groups include two or more heteroaryl rings fusedtogether and monocyclic heteroaryl rings fused to one or more aromaticcarbocyclic rings, non-aromatic carbocyclic rings, and/or non-aromaticcycloheteroalkyl rings. A heteroaryl group, as a whole, can have, forexample, 5 to 40 ring atoms and contain 1-5 ring heteroatoms. Theheteroaryl group can be attached to the defined chemical structure atany heteroatom or carbon atom that results in a stable structure.Generally, heteroaryl rings do not contain O—O, S—S, or S—O bonds.However, one or more N or S atoms in a heteroaryl group can be oxidized(e.g., pyridine N-oxide, thiophene S-oxide, thiophene S,S-dioxide).Examples of heteroaryl groups include, for example, the 5- or 6-memberedmonocyclic and 5-6 bicyclic ring systems shown below:

where T is O, S, NH, N-alkyl, N-aryl, N-(arylalkyl) (e.g., N-benzyl),SiH₂, SiH(alkyl), Si(alkyl)₂, SiH(arylalkyl), Si(arylalkyl)₂, orSi(alkyl)(arylalkyl). Examples of such heteroaryl rings includepyrrolyl, furyl, thienyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl,triazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl, thiazolyl,thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, indolyl, isoindolyl,benzofuryl, benzothienyl, quinolyl, 2-methylquinolyl, isoquinolyl,quinoxalyl, quinazolyl, benzotriazolyl, benzimidazolyl, benzothiazolyl,benzisothiazolyl, benzisoxazolyl, benzoxadiazolyl, benzoxazolyl,cinnolinyl, 1H-indazolyl, 2H-indazolyl, indolizinyl, isobenzofuryl,naphthyridinyl, phthalazinyl, pteridinyl, purinyl, oxazolopyridinyl,thiazolopyridinyl, imidazopyridinyl, furopyridinyl, thienopyridinyl,pyridopyrimidinyl, pyridopyrazinyl, pyridopyridazinyl, thienothiazolyl,thienoxazolyl, thienoimidazolyl groups, and the like. Further examplesof heteroaryl groups include 4,5,6,7-tetrahydroindolyl,tetrahydroquinolinyl, benzothienopyridinyl, benzofuropyridinyl groups,and the like. In some embodiments, heteroaryl groups can be substitutedas described herein.

At various places in the present specification, substituents on achemical group are disclosed in groups or in ranges. It is specificallyintended that the description include each and every individualsubcombination of the members of such groups and ranges. For example,the term “C₁₋₆ alkyl” is specifically intended to individually discloseC₁, C₂, C₃, C₄, C₅, C₆, C₁-C₆, C₁-C₅, C₁-C₄, C₁-C₃, C₁-C₂, C₂-C₆, C₂-C₅,C₂-C₄, C₂-C₃, C₃-C₆, C₃-C₅, C₃-C₄, C₄-C₆, C₄-C₅, and C₅-C₆ alkyl. By wayof other examples, an integer in the range of 0 to 40 is specificallyintended to individually disclose 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29,30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40, and an integer in therange of 1 to 20 is specifically intended to individually disclose 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.Additional examples include that the phrase “optionally substituted with1-5 substituents” is specifically intended to individually disclose achemical group that can include 0, 1, 2, 3, 4, 5, 0-5, 0-4, 0-3, 0-2,0-1, 1-5, 1-4, 1-3, 1-2, 2-5, 2-4, 2-3, 3-5, 3-4, and 4-5 substituents.

As used herein, a “p-type semiconductor material” or a “p-typesemiconductor” refers to a semiconductor material having holes as themajority current carriers. In some embodiments, when a p-typesemiconductor material is deposited on a substrate, it can provide ahole mobility in excess of about 10⁻⁵ cm²/Vs. In the case offield-effect devices, a p-type semiconductor also can exhibit a currenton/off ratio of greater than about 10.

As used herein, an “n-type semiconductor material” or an “n-typesemiconductor” refers to a semiconductor material having electrons asthe majority current carriers. In some embodiments, when an n-typesemiconductor material is deposited on a substrate, it can provide anelectron mobility in excess of about 10⁻⁵ cm²/Vs. In the case offield-effect devices, an n-type semiconductor also can exhibit a currenton/off ratio of greater than about 10.

As used herein, a “dielectric material” has a conductivity in the orderof 10⁻⁶ Scm⁻¹ or less to avoid current leakage to an adjacent electricalconductor.

It will be understand that when two components are described as beingcoupled to each other, the two components can be directly in contact(e.g., directly coupled to each other), or the two components can becoupled to each other via one or more intervening components or layers.

Throughout the specification, a specific stereoisomer may be presentedwhen multiple stereoisomers are possible. In such cases, the specificstereoisomer presented should be understood to represent the differentpossible stereoisomers, unless explicitly stated otherwise. For example,a depiction of a cis-isomer should be understood to represent both thecis- and the trans-isomers, and vice versa.

Linear polymers according to the present teachings generally comprise arepeating unit of formula (A):

wherein:X and Y independently are selected from the group consisting of CH₂,CHR, CR₂, C(O), SiH₂, SiHR, SiR₂, NH, NR, O, and S, wherein

-   -   R is selected from the group consisting of a halogen, —OR^(a),        —C(O)OR^(a), —OC(O)R^(a), —NR^(b)R^(c), —C(O)NR^(b)R^(c),        —OC(O)R^(a), —NR^(b)R^(c), —C(O)NR^(b)R^(c), —OC(O)NR^(b)R^(c),        a C₁₋₁₀ alkyl group, a C₁₋₁₀ haloalkyl group, and an optionally        substituted aryl or heteroaryl group,    -   R^(a) is a C₁₋₁₀ alkyl group or a —Si(C₁₋₁₀ alkyl)₃ group, and    -   R^(b) and R^(c) independently are H or a C₁₋₁₀ alkyl group;        W—Z is CH═CH or

R¹, R², R³, and R⁴ independently are selected from the group consistingof H, —OR^(d), —C(O)OR^(d), —OC(O)R^(d), a C₁₋₁₀ alkyl group, a C₁₋₁₀haloalkyl group, and L-Q, wherein

-   -   L is selected from the group consisting of —O—, —C(O), a        divalent C₁₋₁₀ alkyl group, a divalent C₆₋₁₈ aryl group, a        covalent bond, and combinations thereof,    -   Q is a crosslinkable group comprising an ethenyl moiety, an        ethynyl moiety, a dienyl moiety, an acrylate moiety, a        coumarinyl moiety, an epoxy moiety, or a combination thereof,        and    -   R^(d) is H or a C₁₋₁₀ alkyl group,        provided that at least one of R¹, R², R³, and R⁴ is L-Q; and        m is 0, 1 or 2.

In various embodiments, the present linear polymers can be obtained viaring-opening metathesis polymerization (ROMP) using a norbornene-typemonomer. The simplest norbornene-type monomer isbicyclo[2.2.1]hept-2-ene

which is commonly referred to as norbenene. However, the termnorbornene-type monomer as used herein shall be understood to encompassany substituted norbornene, any substituted or unsubstituted highercyclic derivatives thereof, as well as any analog thereof where thebridging CH₂ group(s) is replaced by a heteroatom (e.g., O or S), acarbonyl group, a silyl group, or an amine group. For example, highercyclic derivatives of norbornene can include:

wherein q is 1 or 2;a norbornene anhydride

anda norbornene dicarboximide

wherein R⁵ can be H, a solubilizing group (e.g., an optionallysubstituted C₁₋₄₀ alkyl, alkenyl, cyclolalkyl, halolalkyl, or arylalkylgroup), or a crosslinkable group (e.g., L-Q).

Monomers useful for preparing the present polymers can be represented byformula (B):

where R¹, R², R³, R⁴, X, Y, and m are as defined herein.

In preferred embodiments, the present linear polymers can comprise arepeating unit of formula (II):

which polymers can be prepared from a monomer represented by formula(I):where L, Q, and X are as defined herein.

For example, in some embodiments, at least one of X and Y can beselected from —CHR—, —CR₂—, —C(O), —SiH₂—, —SiR₂—, —NH—, —NR—, —O— and—S—; where R is as defined herein. In some embodiments, both X and Y canbe —CH₂—.

In various embodiments, the norbornene-type monomer can be substitutedwith one or more L-Q groups to allow crosslinkability. For example, eachL-Q group can be selected from the group consisting of:

wherein R¹ is H or a C₁₋₂₀ alkyl group.

To further illustrate, the present polymers can be prepared viaselective ring-opening metathesis polymerization (ROMP) using, forexample, one of the following monomers:

wherein Q¹ and Q² independently are H or CH₃; R′ is H or OCH₃; and n isan integer from 1 to 10.

Further exemplary monomers include

The above monomers either have been reported in the literature or can beprepared using procedures analogous to those that have been reported inthe literature.

In certain embodiments, the present linear polymer can be a copolymerincluding a repeating unit of formula (A) as described above and one ormore additional repeating units that are distinct from the repeatingunit of formula (A). For example, these additional repeating unitstypically are not derived from a monomer that includes a crosslinkablegroup and can be represented by formula (C)

wherein:X′ and Y′ independently are selected from the group consisting of CH₂,CHR, CR₂, C(O), SiH₂, SiHR, SiR₂, NH, NR, O, and S, wherein

-   -   R is selected from the group consisting of a halogen, —OR^(a),        —C(O)OR^(a), —OC(O)R^(a), —NR^(b)R^(c), —C(O)NR^(b)R^(c),        —OC(O)NR^(b)R^(c), a C₁₋₁₀ alkyl group, a C₁₋₁₀ haloalkyl group,        and an optionally substituted aryl or heteroaryl group,    -   R^(a) is a C₁₋₁₀ alkyl group or a —Si(C₁₋₁₀ alkyl)₃ group, and    -   R^(b) and R^(c) independently are H or a C₁₋₁₀ alkyl group;        W′—Z′ is CH═CH or

R⁶, R⁷, R⁸, and R⁹ independently are H or L′-T, wherein

-   -   L′ is selected from the group consisting of —O—, —C(O), a        divalent C₁₋₁₀ alkyl group, a divalent C₆₋₁₈ aryl group, a        covalent bond, and combinations thereof; and    -   T is H, OH, a C₁₋₁₀ alkyl group, a C₁₋₁₀ haloalkyl group, a        C₁₋₁₀ alkoxy group, an OC(O)(C₁₋₁₀ alkyl) group, a Si(OC₁₋₁₀        alkyl)₃ group, and a phenyl group optionally substituted 1-5        groups independently selected from halo, OH, a C₁₋₁₀ alkyl        group, a C₁₋₁₀ haloalkyl group, and a C₁₋₁₀ alkoxy group; and        m′ is 0, 1 or 2.

Monomers that give rise to these additional repeating units (C) can berepresented by formula (D):

wherein X′, Y′, R⁶, R⁷, R⁸, R⁹, and m′ are as defined herein. Forexample, monomers represented by formula (D) can be selected from thegroup consisting of:

Additional embodiments of monomers of formula (B) or (D) can be preparedaccording to procedures described in Chem. Letts., 36(9): 1162-1163(2007); Chem. Comm., 16:1755-1756 (1998); and Chemische Berichte,111(4): 1264-1274 (1978), the entire disclosure of each of which isincorporated by reference herein for all purposes.

Further embodiments of monomers of formula (B) or (D) can be preparedvia alkyne metathesis using procedures described in, for example,Synlett, 15: 2333-2336 (2003); Angew. Chem., 106(6): 664-666 (1994);Angew. Chem., Int. Ed. Engl., 33(6): 636-638 (1994); J. Chem. Soc.,457-463 (1981); J. Org. Chem., 76(16): 6591-6957 (2011); European J.Org. Chem., 24: 4178-4192 (2008); Org. Letts., 6(24): 4543-4546 (2004);and J. Fluorine Chem., 73(1): 61-67 (1995); the entire disclosure ofeach of which is incorporated by reference herein for all purposes.

In certain embodiments, the present linear polymer can be derived partlyfrom a norbornene anhydride or norbornene dicarboximide co-monomer andaccordingly, such linear polymer can include a repeating unitrepresented by

wherein R⁵ is selected from the group consisting of H, L′-T, and L′-Q,wherein

-   -   L is selected from the group consisting of —O—, —C(O), a        divalent C₁₋₁₀ alkyl group, a divalent C₆₋₁₈ aryl group, a        covalent bond, and combinations thereof;    -   L′ is selected from the group consisting of —O—, —C(O), a        divalent C₁₋₁₀ alkyl group, a divalent C₆₋₁₈ aryl group, a        covalent bond, and combinations thereof;    -   Q is a crosslinkable group comprising an ethenyl moiety, an        ethynyl moiety, a dienyl moiety, an acrylate moiety, a        coumarinyl moiety, an epoxy moiety, or a combination thereof;        and    -   T is H, OH, a C₁₋₁₀ alkyl group, a C₁₋₁₀ haloalkyl group, a        C₁₋₁₀ alkoxy group, an OC(O)(C₁₋₁₀ alkyl) group, a Si(OC₁₋₁₀        alkyl)₃ group, and a phenyl group optionally substituted 1-5        groups independently selected from halo, OH, a C₁₋₁₀ alkyl        group, a C₁₋₁₀ haloalkyl group, and a C₁₋₁₀ alkoxy group.

In certain embodiments, the present linear polymer can be derived partlyfrom a norbornene monomer substituted with a polyhedral oligomericsilsesquioxane (POSS) group. Examples of such monomers include:

where Cp is cyclopentyl, i-Bu is iso-butyl, Et is ethyl, Cy iscyclohexyl and Me is methyl.

In addition to being polymerizable via ring-opening metathesispolymerization reaction, it should be noted that monomers falling withinformula (I) also can undergo vinyl-addition polymerization as shown bythe scheme below:

where the polymerization reaction is initiated by addition catalystssuch as the organo nickel or palladium complexes described in U.S. Pat.No. 5,468,819. Despite being formed by the same or similar monomer,these addition polymers are structurally distinguishable over the linearpolymers according to the present teachings, which are obtained viaring-opening metathesis polymerization (ROMP) reaction. Most notably,because of the different polymerization mechanism (due to the use ofdifferent catalysts/initiators), the linear polymers according to thepresent teachings always include unsaturated bonds in the backbone, asillustrated below:

while addition polymers do not have any unsaturated bonds in thebackbone. Further, the repeating unit in an addition polymer retains thesame number of rings as the monomer (for example, a bicyclic monomerresults in a bicyclic repeating unit), while the repeating unit in alinear polymer has one ring less than the monomer due to ring opening.

To achieve the linear polymers of formula (A), selective ring-opening ofthe monomers described herein is required. The ring-openingpolymerization of norbornene-type monomer has been studied extensively.For example, a class of catalysts/catalytic systems that can be usefulfor preparing the linear polymers according to the present teachings isbased upon the metal chloride ReCl₅. A co-catalyst such as (CH₃)₄Sn canbe used to increase yield and improve purity.

Examples of additional useful catalytic systems include WCl₆—SiAll₄,WOCl₄—SiAll₄, WOCl₄—SiMe₂All₂, and WCl₆—H₂O—SiMe₂All₂+H₂O/WCl₆(All=allyl).

Further useful catalysts/catalytic systems are described in Makromol.Chem., 130: 153-165 (1969) and U.S. Pat. No. 5,198,511, the entiredisclosure of each of which is incorporated by reference herein for allpurposes.

Accordingly, using appropriate catalysts or catalytic systems known inthe art such as, but not limited to, those explicitly described herein,monomers of formula (I) can be used to prepare linear polymers offormula (II) via selective ring-opening metathesis polymerization. Invarious embodiments, the present polymers can be high molecular weightpolymers, where n is an integer in the range of 500 to 500,000.

In embodiments where the linear polymer is a copolymer, the co-monomer(D) can be present in an amount of from about 0.01% to about 50% byweight, preferably from about 0.1% to about 20% by weight, morepreferably from about 1% to about 10% by weight. In certain embodiments,such a co-polymer also can be end-functionalized with a crosslinkableacrylate group as described above.

Prior to crosslinking, the optionally end-functionalized linearhomopolymers and co-polymers according to the present teachingsgenerally are soluble in common organic solvents but can becomesignificantly less soluble or insoluble in the same solvents afterundergoing crosslinking. As used herein, a compound can be consideredsoluble in a solvent when at least 1 mg of the compound can be dissolvedin 1 ml of the solvent. Compounds wherein less than 1 mg of the compoundcan be homogeneously dissolved in 1 ml of the solvent are consideredinsoluble.

More specifically, the present polymers (prior to crosslinking) can havesatisfactory solubility in various common organic solvents, therebyaffording formulations that are suitable for solution-phase processes.In certain embodiments, the present polymers can have satisfactorysolubility in organic solvents that are orthogonal to those solvents(e.g., aromatic or polar chlorinated solvents) typically used to processcommon organic semiconducting molecules or polymers. This allows, forexample, the fabrication of a solution-processed top-gate transistor,where the organic solvent used to dissolve the present polymers does notdamage (i.e., dissolve, delaminate, swell, or otherwise physicallydisturb) or adversely affect the semiconducting properties of anunderlying organic semiconductor material. Examples of organic solventsthat can be used to formulate the present linear polymers includealiphatic hydrocarbons such as hexanes, cyclopentane, cyclohexane,n-nonane, n-decane, n-undecane, n-dodecane; alcohol solvents such asmethanol, ethanol, isopropanol, 1-butanol, 2-ethoxymethanol,3-methoxypropanol, cyclopentanol, cyclohexanol, and heptanol; ketonesolvents such as acetone, acetylacetone, methyl ethyl ketone, methylisobutyl ketone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone,cyclopentanone, and cyclohexanone; ester solvents such as ethyl acetate,propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate,cyclohexyl acetate, heptyl acetate, ethyl propionate, propyl propionate,butyl propionate, isobutyl propionate, propylene glycol monomethyl etheracetate, methyl lactate, ethyl lactate and γ-butyrolactone; ethersolvents such as diisopropyl ether, dibutyl ether, ethyl propyl ether,anisole, phenetole, and veratrole; and amide solvents such asN-methylpyrrolidinone and dimethylacetamide. These solvents can be usedeither singly or in combination, or as mixtures with water.

Accordingly, the present polymers can be mobilized in a liquid medium toprovide a composition (a coating formulation) for forming a thin filmmaterial. The composition can be a solution, a dispersion, a suspension,an emulsion, or a gel, although in most embodiments, the composition isa solution or a dispersion suitable for solution-phase processes. Theliquid medium can include solid and/or gaseous components, that is, theliquid medium can be in a vapor or gaseous form. As such, the term“liquid medium” can include a vaporized liquid medium. The term“mobilized in a liquid medium” broadly means that the designated liquidmedium causes a designated solid to take on properties of a liquid orvapor. For example, the solid can be dissolved in the liquid medium toform a single-phase solution, or the solid can be dispersed in theliquid medium to form a two-phase dispersion. In other embodiments, thesolid and the liquid medium can be combined together to form anemulsion, a suspension, a gel, or even micelles. As used herein, theterm “solution” means that a substantial proportion of a designatedsolute has formed a single phase with a designated solvent, but asubstantial solid, liquid and/or gaseous second phase that can includedispersed particulate matter also can be present.

In addition to the present polymers, the coating formulation can includeother components that can be used to selectively modify certainproperties such as the viscosity of the coating formulation, or thedielectric properties, thermal stability, and/or glass transitiontemperature of the film material to be formed. The coating formulationalso can include initiators and/or sensitizers such as those describedhereinabove to modify the crosslinkability of the present polymers.Accordingly, in some embodiments, the coating formulation can includeone or more additives independently selected from viscosity modulators,detergents, dispersants, binding agents, compatibilizing agents, curingagents, initiators, sensitizers, humectants, antifoaming agents, wettingagents, pH modifiers, biocides, and bactereriostats. For example,surfactants and/or polymers (e.g., polystyrene, polyethylene,poly-alpha-methylstyrene, polyisobutene, polypropylene,polymethylmethacrylate, and the like) can be included as a dispersant, abinding agent, a compatibilizing agent, and/or an antifoaming agent. Insome embodiments, the coating formulation can include another lineardielectric polymer, a metal oxide, a silane crosslinker, an acrylatecrosslinker, and/or combinations thereof, which can be used to prepare ablend dielectric material. For example, metal oxide fillers can be usedto provide a higher dielectric constant. Fillers that have a highdielectric constant include metal oxides such as SiO₂, Al₂O₃, TiO₂, andthe like; nitrides such as Si₃N₄; and paraelectric ceramic fillers suchas barium titanate, strontium titanate, and lead zirconate.

As used herein, “solution-processable” or “solution-processed” refers tothe ability of a compound, for example, the present polymers, to beprocessed via various solution-phase processes. A coating formulationcomprising the present polymers can be deposited on a substrate, such asan electrically conductive material (e.g., source, drain, or gateelectrodes in a transistor) or a semiconductor material (e.g., thecharge-carrying layer in a transistor), via various solution-phasedeposition methods known in the art. In various embodiments, thesolution-phase process can be selected from spin-coating, slot coating,printing (e.g., inkjet printing, screen printing, pad printing, offsetprinting, gravure printing, flexographic printing, lithographicprinting, mass-printing and the like), spray coating, electrospraycoating, drop casting, dip coating, and blade coating. Spin-coatinginvolves applying an excess amount of the coating solution onto thesubstrate, then rotating the substrate at high speed to spread the fluidby centrifugal force. The thickness of the resulting film prepared bythis technique can be dependent on the spin-coating rate, theconcentration of the solution, as well as the solvent used. Printing canbe performed, for example, with a rotogravure printing press, aflexoprinting press, pad printing, screen printing or an ink jetprinter. The thickness of the resulting film as processed by theseprinting methods can be dependent on the concentration of the solution,the choice of solvent, and the number of printing repetitions. Ambientconditions such as temperature, pressure, and humidity also can affectthe resulting thickness of the film. Depending on the specific printingtechniques used, printing quality can be affected by differentparameters including, but not limited to, rheological properties of theformulations/compositions such as tension energy and viscosity. Fornoncontact printing techniques such as inkjet printing, the solubilityrequirement generally can be less stringent and a solubility range aslow as about 1-4 mg/ml can suffice. For gravure printing, a highersolubility range may be necessary, often in the range of about 50-100mg/ml. Other contact printing techniques such as screen-printing andflexo printing can require even higher solubility ranges, for example,about 100-1000 mg/ml

The resulting film can take various forms including a wafer, a layer, asheet, or an elongated web. Thin film materials based upon a polymeraccording to the present teachings can be monolithic (composed of asingle homogenous layer) or can have multiple sublayers, where themultiple sublayers can have identical (homogeneous) or different(heterogeneous) chemical compositions.

In various embodiments, crosslinking of the present polymers isperformed by radiation. For example, exposure to ultraviolet light at awavelength of about 250-500 nm (e.g., between about 300 nm and about 450nm) can be used. In embodiments where the present polymers areend-functionalized (e.g., with an acrylate group), the end functionalgroup can be used for an additional crosslinking step by radiation. Forexample, exposure to light of wavelength λ₁ can mostly crosslink thepolymer backbone, whereas exposure to light of wavelength λ₂ can promotecrosslinking of the end functional group. Photocrosslinking, in general,also can be achieved by other types of radiation, for example, with ionbeams of charged particles, and electron beams from radioactive sources.Further, in certain embodiments, initiators can be used (regardless ofwhether the present linear polymers are end-functionalized or not). Forexample, the initiators can be present as an additive in the coatingformulation comprising the present polymers. Examples of initiators caninclude radical initiators such as azobisisobutyronitrile (AIBN),photoacid generators (PAGs) such as triphenylsulfonium triflate, radicalphotoinitiators such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide(TPO), or photosensitizers such as benzophenone and1-chloro-4-propoxy-9H-thioxanthen-9-one. For example, embodiments wherethe L-Q group is an epoxide group can be photocrosslinked when used withvarious PAGs. Some commercially available PAGs are:

In some embodiments, the present linear polymers can beend-functionalized with a photocrosslinkable group such as an acrylategroup or a cinnamate group. For example, end-functionalized linearpolymers according to the present teachings can be prepared by reactingthe metal-carbene end group of the linear polymer with an acrylate via aselective Wittig-type reaction.

Additional acrylates suitable for end-functionalizing the present linearpolymers are known in the art, including those described inInternational Publication No. WO 2010/136385, the entire disclosure ofwhich is incorporated by reference herein for all purposes. The acrylateend group provides an additional mechanism for crosslinking,specifically, via click chemistry (such as thiol-ene coupling) or freeradical additions that can be initiated by initiators with or withoutsensitizers. Examples of initiators and sensitizers are provided inInternational Publication No. WO 2010/136385. Chemistries and exemplarychemical groups for end-functionalizing ROMP polymers are described in,for example, Nature Chemistry, 1: 537 (2009), the entire disclosure ofwhich is incorporated by reference herein for all purposes.

In some embodiments, the present polymers can be thermally cured toprovide improved properties such as increased glass transitiontemperature (T_(g)), which can lead to enhanced thermal stability,improved adhesion, and/or smoother interface with an adjacent material(e.g., a semiconductor material). For example, the crosslinkable groupL-Q can include an epoxide group.

In certain embodiments, the linear polymer of formula (II) can undergoepoxidation to provide an epoxide polymer which is also thermallycrosslinkable. For example, the linear polymer of formula (II) can bereacted with a strong oxidizing agent including various peroxy acidssuch as meta-chloroperoxybenzoic acid (mCPBA) to provide an epoxidepolymer as shown in the scheme below:

In some embodiments, it can be preferable to anneal the thin filmmaterial for an extended period of time (e.g., more than or about 10minutes, more than or about 20 minutes, or more than or about 30minutes), for example, if a larger dielectric constant is desirable. Invarious embodiments, dielectric materials according to the presentteachings can have a dielectric constant of at least about 2.3,preferably between about 2.5 and about 10, more preferably between about3 and about 5.

The present linear polymers can be thermally cured at differenttemperatures for various periods of time into a crosslinked materialwhich is resistant to the mother solvent used to solution-process thelinear polymer prior to thermal crosslinking. For example, the linearpolymer can be deposited as a thin film which subsequently can bethermally cured in air or oxygen at a temperature of lower than or about350° C., of lower than or about 300° C., at a temperature of lower thanor about 200° C., at a temperature of lower than or about 180° C., at atemperature of lower than or about 150° C., at a temperature of lowerthan or about 140° C., or at a temperature of lower than or about 130°C., for as brief as about 8 minutes or less, and results in a physicallyrobust crosslinked polymeric matrix with good interfacial propertiessuitable for further device processing such as patterning and subsequentsolution-phase processes (e.g., to form/deposit overlying layers such asthe semiconductor layer in a bottom-gate TFT structure or the gate layerfor a top-gate TFT structure).

In some embodiments, the linear polymer of formula (II) can be partiallyhydrogenated, then thermally crosslinked. Particularly, the linearpolymer of formula (II) can be partially hydrogenated using eitherhomogenous or heterogeneous transition metal catalysts such as Pd and Rucomplexes. The partial hydrogenation reaction can be performed underatmospheric pressure and at room temperature (e.g., standard ambienttemperature and pressure, at about 25° C. and about 1 atm), or atelevated temperatures and/or with pressurized hydrogen. The extent ofhydrogenation can be monitored using various methods known in the art.For example, the degree of hydrogenation can be determined from infraredspectra obtained with samples taken during various points of thehydrogenation reaction. In various embodiments, the present polymers canbe partially hydrogenated such that no more than about 80%, andpreferably no more than about 50%, of the unsaturated bonds in thebackbone of the linear polymer are hydrogenated. Partial hydrogenationof the present linear polymer can lower the leakage current density ofthe polymer while keeping the linear polymer readily thermallycrosslinkable. As described above, the partially hydrogenated linearpolymer can be thermally cured at a temperature of lower than or about350° C., of lower than or about 300° C., at a temperature of lower thanor about 200° C., at a temperature of lower than or about 180° C., at atemperature of lower than or about 150° C., at a temperature of lowerthan or about 140° C., or at a temperature of lower than or about 130°C., for as brief as about 8 minutes or less, and results in a physicallyrobust thin film material with good interfacial properties suitable forfurther device processing.

Subsequent to the formation of the crosslinked matrix, the thin filmmaterial of the present teachings can be subjected to further patterningand processing steps, by which additional layers, including additionaldielectric, semiconductor and/or conducting layers, can be formedthereon.

The present polymers can have excellent electrically insulatingproperties and a low leakage current density, which enable their use asdielectrics. Leakage current density typically is defined as a vectorwhose magnitude is the leakage current per cross-sectional area. As usedherein, “leakage current” refers to uncontrolled (“parasitic”) currentflowing across region(s) of a semiconductor structure or device in whichno current should be flowing, for example, current flowing across thegate dielectric in a thin-film transistor device. As known by thoseskilled in the art, the leakage current density of a dielectric materialcan be determined by fabricating a standardmetal-insulator-semiconductor (MIS) and/or metal-insulator-metal (MIM)capacitor structures with the dielectric material, then measuring theleakage current, and dividing the measured current by the area of themetal electrodes.

In various embodiments, the present polymers can have very low leakagecurrent densities as measured from standard MIS and MIM capacitorstructures. For example, dielectric materials prepared from a polymeraccording to the present teachings can have a leakage current density ofless than or equal to about 1×10⁻⁶ A/cm² at E=2 MV/cm, less than orequal to about 1×10⁻⁷ A/cm² at E=2 MV/cm, less than or equal to about1×10⁻⁸ A/cm² at E=2 MV/cm, less than or equal to about 8×10⁻⁹ A/cm² atE=2 MV/cm, less than or equal to about 7×10⁻⁹ A/cm² at E=2 MV/cm, lessthan or equal to about 6×10⁻⁹ A/cm² at E=2 MV/cm, less than or equal toabout 4×10⁻⁹ A/cm² at E=2 MV/cm, less than or equal to about 2×10⁻⁹A/cm² at E=2 MV/cm, or less than or equal to about 1×10⁻⁹ A/cm² at E=2MV/cm. Dielectric materials prepared from the present polymers also canwithstand very high breakdown voltages (i.e., the maximum voltagedifference that can be applied across the dielectric before it breaksdown and begins to conduct). For example, dielectric materials of thepresent teachings can withstand a breakdown voltage of 4 MV/cm orhigher, a breakdown voltage of 6 MV/cm or higher, or a breakdown voltageof 7 MV/cm or higher.

As described hereinabove, because the present polymers can be soluble insolvents that are orthogonal to those commonly used to dissolve organicor inorganic semiconducting compounds, the present polymers can be used,in whole or in part, as the dielectric layer of a solution-processedorganic field-effect transistor. A typical field-effect transistor (FET)includes a number of layers and can be configured in various ways. Forexample, a FET can include a substrate, a dielectric layer, asemiconductor layer, source and drain electrodes in contact with thesemiconductor layer, and a gate electrode adjacent to the dielectriclayer. When a potential is applied on the gate electrode, chargecarriers are accumulated in the semiconductor layer at an interface withthe dielectric layer. As a result, a conductive channel is formedbetween the source electrode and the drain electrode and a current willflow if a potential is applied to the drain electrode.

FIG. 1 illustrates the four common types of FET structures: (a)bottom-gate top-contact structure, (b) bottom-gate bottom-contactstructure, (c) top-gate bottom-contact structure, and (d) top-gatetop-contact structure. As shown in FIG. 1, a FET can include adielectric layer (e.g., shown as 8, 8′, 8″, and 8″ in FIGS. 1a, 1b, 1c,and 1d , respectively), a semiconductor/channel layer (e.g., shown as 6,6′, 6″, and 6″ in FIGS. 1a, 1b, 1c, and 1d , respectively), a gatecontact (e.g., shown as 10, 10′, 10″, and 10″ in FIGS. 1a, 1b, 1c, and1d , respectively), a substrate (e.g., shown as 12, 12′, 12″, and 12″ inFIGS. 1a, 1b, 1c, and 1d , respectively), and source and drain contacts(e.g., shown as 2, 2′, 2″, 2″, 4, 4′, 4″, and 4″ in FIGS. 1a, 1b, 1c,and 1d , respectively). One or more optional layers also can be present.For example, an optional buffer layer can be deposited on top of thesubstrate to improve the wetting and crystallization of an overlyinglayer. An optional surface-modifying film can be disposed on the gateelectrode.

Using an example of a bottom-gate top-contact thin film transistor, FIG.2 illustrates where the organic material of the present teaching can beemployed: in layer 1 (as a surface modifier), layer 2 (as the gatedielectric), layer 3 (as an additive to the semiconductor), and/orencapsulation layer 4 (as an etch-stop/blocking/passivation/barriermaterial).

Accordingly, the present polymers can be deposited as a thin filmmaterial adjacent to a semiconductor layer and function as thedielectric layer in a thin film transistor. Specifically, the thin filmmaterial can be coupled to the semiconductor thin film layer on one sideand an electrically conductive component (i.e., a gate electrode) on theopposite side. The thickness of the dielectric layer typically rangesfrom about 10 nm to about 5000 nm, preferably from about 50 nm to about1000 nm, and more preferably from about 200 nm to about 500 nm. In someembodiments, one or more interlayers can be present between thesemiconductor layer and the dielectric layer comprising the presentpolymers. The interlayer(s) can be prepared from one or more lineardielectric polymers, examples of which are provided hereinbelow.

In some embodiments, the dielectric layer can be a multi-layer laminatehaving two or more layers of dielectric materials sequentially depositedon top of each other (although one or more interlayers can be present),where at least one of the layers is prepared from a compositionincluding a polymer according to the present teachings. For example, themulti-layer laminate can include at least one layer prepared from acomposition including the present polymers alone in a liquid medium, andat least one layer prepared from a linear dielectric polymer or aninorganic (e.g., metal oxide) dielectric material. In embodiments wherethe dielectric material includes organic and inorganic sublayers, aninterlayer can be present to improve adhesion between the sublayers.

Examples of linear dielectric polymers that can be used in combinationwith the present polymers (either in the same dielectric layer or in aseparate dielectric layer) can include, without limitations, fluorinatedpara-xylene, fluoropolyarylether, fluorinated polyimide, polystyrene,poly(α-methyl styrene), poly(α-vinylnaphthalene), poly(vinyltoluene),polyethylene, cis-polybutadiene, polypropylene, polyisoprene,poly(4-methyl-1-pentene), poly(tetrafluorethylene),poly(chlorotrifluoroethylene), poly(2-methyl-1,3-butadiene),poly(p-xylylene), poly(α-α-α′-α′-tetrafluoro-p-xylylene),poly[1,1-(2-methyl propane) bis (4-phenyl) carbonate], poly(cyclohexylmethacrylate), poly(4-chlorostyrene), poly(2,6-dichlorostyrene),poly(4-bromostyrene), poly(2,6-dimethyl-1,4-phenylene ether),polyisobutylene, poly(vinyl cyclohexane), poly(arylene ether),polyphenylene, poly(ethylene/tetrafluoroethyelene),poly(ethylene/chlorotrifluoroethylene), fluorinated ethylene/propylenecopolymer, polystyrene-co-α-methyl styrene, ethylene/ethyl acetatecopolymer, poly(styrene/butadiene), poly(styrene/2,4-dimethyl styrene),polypropylene-co-1-butene, poly(methyl methacrylate), poly(ethylmethacrylate), poly(2-hydroxyethyl methacrylate), poly(butylmethacrylate), poly(hexyl methacrylate), poly(benzyl methacrylate),poly(vinyl phenol), poly(vinyl alcohol), poly(vinylalcohol-co-ethylene), poly(isobutylene/methyl methacrylate), poly(vinylphenol/methyl methacrylate), poly(vinyl chloride), polysaccharides suchas 2-hydroxyethyl cellulose, cellulose actate, cellullose acetatebutyrate, ethyl cellulose; cyanated (ethoxylated) polysaccharides suchas cyanopullulan (e.g., CYMM®), benzocyclobutene-based polymers,poly(2-vinylpyridine), poly(4-vinylpyridine),poly(4-vinylpyridine-co-butyl methacrylate),poly(4-vinylpyridine-co-styrene), poly(1-vinylpyrrolidone-co-styrene),poly(1-vinylpyrrolidone-co-vinyl acetate), poly(vinylidine fluoride),polyacrylonitrile, poly(acrylonitrile-co-butadiene-co-styrene),poly(acrylonitrile-co-methyl acrylate), polyacrylamide,poly(N-isopropylacrylamide), poly(2-ethyl-2-oxazoline),polyvinylpyrrolidone, poly(pentafluorostyrene), poly(dimethylsiloxane),poly(tetrahydrofuran), poly(methyl vinyl ether), poly(methyl vinylether-alt-maleic anhydride), poly(ethyl vinyl ether),poly(ethylene-alt-maleic anhydride), poly(allylamine),poly(ethyleneimine), poly(vinyl acetate), poly(vinyl cinnamate),poly(vinyl stearate), poly(vinyl propionate), poly(vinyl formate),poly(ethylene glycol), poly(propylene glycol),poly(styrene-co-acrylonitrile), poly(maleic anhydride-alt-1-octadecane),poly(tetrahydrofuryl methacrylate), poly(Bisphenol A carbonate),poly(propylene carbonate), poly(1,4-butylene terephthalate),poly(diallyl isophthalate), poly(hexafluoropropylene oxide),poly(fluoropropylene oxide-co-perfluoroformaldehyde), and combinationsthereof. In addition, perfluoro(1-butenyl vinyl ether) homocyclopolymers(for example, those under the trade name CYTOP®) can be used. Examplesof such fluorinated cyclopolymers include those having one of thefollowing structures:

Poly[4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole-co-tetrafluoroethylene(commercially available under the trade name Teflon® AF 2400) having thefollowing structure also can be used:

The semiconductor layer can comprise an organic semiconductor materialprepared from an organic semiconducting molecule or polymer. Examplesinclude various fused heterocycles, aromatic hydrocarbons,polythiophenes, fused (hetero)aromatics (e.g., perylene imide andnaphthalene imide small molecule or polymers), and other such organicsemiconductor compounds or materials, whether p-type or n-type,otherwise known or found useful in the art. For example, thesemiconductor component can be prepared from one or more compoundsand/or polymers as described in U.S. Pat. Nos. 6,585,914, 6,608,323,6,991,749, 7,374702, 7,528,176, 7,569,693, 7,605,225, 7,671,202,7,893,265, 7,892,454, 7,902363, 7,928,249, 7,947,837, 8,022,214; andInternational Publication Nos. WO2009/098254, WO2009/098252,WO2009/098253, WO2009/098250, WO2010/117449, and WO2011/082234, thedisclosure of each of which is incorporated by reference herein. In someembodiments, the semiconductor layer can comprise an inorganicsemiconductor material such as silicon, germanium, gallium arsenide,various metal oxides and metal chalcogenides known in the art, and thelike. Examples of metal oxide semiconductors include indium oxide(In₂O₃), indium zinc oxide (IZO), zinc tin oxide (ZTO), indium galliumoxide (IGO), indium-gallium-zinc oxide (IGZO), indium tin zinc oxide(ITZO), tin oxide (SnO₂), and zinc oxide (ZnO). Examples of metalchalcogenide semiconductors include cadmium sulfide (CdS), cadmiumselenide (CdSe), and the like. Solution-phase processed metal oxides andmetal chalcogenides are described in, for example, U.S. Pat. No.8,017,458, the entire disclosure of which is incorporated by referenceherein for all purposes. Alternatively, the semiconductor layer cancomprise a vapor-phase processed (e.g., sputtered) metal oxide orchalcogenide.

In some embodiments, the present linear polymers can be a component(e.g., as an additive) in the semiconductor layer. Specifically, boththe semiconductor (SC) and the polymer (Pol) can be dissolved in asolvent in which both materials are soluble. Typical totalconcentrations are from about 2 mg/ml to about 20 mg/ml, preferablybetween about 5 mg/ml and about 15 mg/ml. The weight ratio between thesemiconductor and the polymer (SC:Pol, w:w) typically can range fromabout 10:1 to about 1:10, preferably from about 8:2 to about 2:8, morepreferably from about 6:4 to about 4:6. The formulation can bespin-coated and the corresponding semiconducting layer film can beannealed at temperatures at which the polymers of the present teachingsdo not crosslink. Alternatively, the Pol portion of the semiconductorlayer film can be crosslinked by heating alone, by radiation alone, byheating followed by radiation, or by radiation followed by heating. Forexample, the semiconductor layer can be prepared from a compositioncomprising one of the organic semiconducting molecules or polymerslisted hereinabove and at least one of the present linear polymers,thereby providing a blend organic semiconductor material. In particularembodiments, the semiconductor layer can be prepared from a compositioncomprising a small-molecule organic semiconducting compound (such as,but not limited to, any of the small-molecule OSCs listed hereinabove)and a linear polymer according to the present teachings as an additive.

A dielectric material according to the present teachings can be preparedby dissolving one or more polymers described herein in an organicsolvent to provide a dielectric composition, depositing (e.g., byspin-coating or printing) the dielectric composition onto a substrate,and optionally performing at least one curing step to form a dielectricmaterial. For example, the curing step can involve heating at atemperature within the range of about 100° C. and about 350° C.(preferably between about 120° C. and about 250° C.) for a durationbetween about 2 minutes and about 60 minutes (preferably between about 5minutes and about 30 minutes). The curing step also can involveirradiation (e.g., with ultraviolet light). In certain embodiments, oneor more metal oxides can be added to the dielectric composition prior tothe depositing step. In certain materials, one or more linear dielectricpolymers can be added to the dielectric composition prior to thedepositing step. In certain embodiments, one or more crosslinkers can beadded to the dielectric composition prior to the depositing step. Incertain materials, one or more photoacid generators can be added to thedielectric composition prior to the depositing step. An organicsemiconductor layer can be formed via a solution-phase process prior orafter the formation of the dielectric layer. For example, the organicsemiconductor layer can be formed from a composition comprising anorganic semiconducting molecule or polymer in an organic solvent that isorthogonal to the organic solvent in the dielectric composition. Aninorganic semiconductor can be formed by vapor deposition such assputtering.

In some embodiments, a multi-layer dielectric material according to thepresent teachings can be prepared by dissolving one or more polymersdescribed herein in an organic solvent to provide a dielectriccomposition, where the dielectric composition optionally can include atleast one of a linear dielectric polymer, a metal oxide, and acrosslinker; depositing (e.g., by spin-coating or printing) thedielectric composition onto a substrate to form a first layer; anddepositing a composition that includes a linear dielectric polymer or ametal oxide to form a second layer. After each depositing step, a curingstep can be performed, e.g., by heating and optionally irradiation usingparameters described herein. An organic semiconductor layer can beformed via a solution-phase process prior or after the formation of themulti-layer dielectric layer. For example, the organic semiconductorlayer can be formed from a composition comprising an organicsemiconducting molecule or polymer in an organic solvent that isorthogonal to the organic solvent in the dielectric composition. Aninorganic semiconductor can be formed by vapor deposition such assputtering.

Crosslinked thin film materials prepared from the present polymers alsocan be used as a passivation layer in a thin film transistor given theirbarrier properties to moisture and oxygen. When used as a passivationlayer, the thin film material can have a thickness in the range of about0.2 μm to about 5 The passivation layer can be prepared by dissolvingone or more polymers described herein in an organic solvent to provide acoating formulation, depositing (e.g., by spin-coating or printing) thecoating formulation onto a substrate (e.g., overlying the source anddrain electrodes), and optionally performing at least one curing step toform a passivation layer. The curing step can be induced by heat orradiation. For example, the curing step can involve heating at atemperature within the range of about 100° C. and about 350° C.(preferably between about 120° C. and about 250° C.) for a time periodbetween about 2 minutes and about 60 minutes (preferably between about 5minutes and about 30 minutes). The curing step also can involveirradiation (e.g., with ultraviolet light). By using the presentcrosslinked organic materials, which can provide improved moisture- andoxygen-blocking properties, as the passivation layer, the thin filmtransistor can achieve better device reliability. In addition, becausethe present linear polymers can be soluble in solvents that areorthogonal to those typically used to deposit organic semiconductingmolecules or polymers, a passivation layer comprising the present linearpolymers can be formed via a solution-phase process on top of the sourceand drain electrodes in a top-contact transistor structure withoutdamaging the organic semiconductor channel region.

Because the present polymers can be crosslinked at relatively lowtemperatures (e.g., below about 160° C.) or by radiation, they arecompatible with a large variety of substrates, including plastic,flexible substrates that have a low temperature resistance. Examples ofsuch flexible substrates include polyesters such as polyethyleneterephthalate, polyethylene naphthalate, polycarbonate; polyolefins suchas polypropylene, polyvinyl chloride, and polystyrene; polyphenylenesulfides such as polyphenylene sulfide; polyamides; aromatic polyamides;polyether ketones; polyimides; acrylic resins; polymethylmethacrylate,and blends and/or copolymers thereof. In some embodiments, the substratecan be an inexpensive rigid substrate that has relatively low heatand/or chemical resistance. For example, the present organic thin filmscan be coupled to an inexpensive soda lime glass substrate, as opposedto more expensive and higher heat and/or chemical resistant glasssubstrates such as quartz and VYCOR®. In embodiments where a very highdegree of crosslinking is desirable, higher crosslinking temperatures(e.g., about 350° C.) may be used, in which case, morethermally-resistant plastic substrates or flexible glasses or metals canbe used. Substrate-gate materials commonly used in thin-film transistorsinclude doped silicon wafer, tin-doped indium oxide on glass, tin-dopedindium oxide on polyimide or mylar film, aluminum or other metals aloneor coated on a polymer such as polyethylene terephthalate, a dopedpolythiophene, and the like.

Accordingly, the present teachings also relate to electronic, optical,or optoelectronic device comprising an organic layer comprising acrosslinked matrix of a linear polymer of formula (A), where the organiclayer can be in contact or coupled to a semiconductor layer (e.g., anorganic or inorganic semiconductor layer) and/or a conductive component(e.g. a metallic contact that functions as either the source, drain, orgate electrode) either directly or via optionally present interveninglayer(s) such as a protective or surface modifying interlayer. Invarious embodiments, the device can be a transistor device, for examplean organic thin film transistor (OTFT) (more specifically, an organicfield effect transistor (OFET) or an organic light-emitting transistor(OLET)) or a semiconductor oxide thin film transistor (SOTFT). Thesource and drain electrodes as well as the gate electrode can be madeusing various deposition techniques. For example, the source and drainelectrodes can be deposited through a mask, or can be deposited thenetched. Suitable deposition techniques include electrodeposition,vaporization, sputtering, electroplating, coating, laser ablation andoffset printing, from metal or metal alloy including copper, aluminum,gold, silver, platinum, palladium, and/or nickel, or an electricallyconductive polymer such as polyethylenethioxythiophene (PEDOT).

An aspect of the present teachings relates to a thin film transistordevice including a dielectric layer comprising a dielectric material asdescribed herein, a semiconductor layer, a gate electrode, a sourceelectrode, and a drain electrode. The dielectric layer typically isdisposed between the semiconductor layer and the gate electrode.Depending on the device geometry, the source and drain electrodes can bedisposed above the semiconductor layer (top-contact), or thesemiconductor layer can be disposed above the source and drainelectrodes (bottom-contact).

Another aspect of the present teachings relates to methods forfabricating field effect transistors that include a dielectric materialof the present teachings. The dielectric materials of the presentteachings can be used to fabricate various types of field effecttransistors including, but not limited to, top-gate top-contactstructures, top-gate bottom-contact structures, bottom-gate top-contactstructures, and bottom-gate bottom-contact structures.

In some embodiments, the method can include depositing a dielectriccomposition according to the present teachings onto a substrate (gate)to form a dielectric layer, wherein the dielectric composition includesone or more linear polymers described herein dissolved in a firstsolvent; depositing a semiconducting composition onto the dielectriclayer to form a semiconductor layer, where the semiconductingcomposition includes one or more semiconducting compounds (e.g., smallmolecule compounds or polymers) dissolved in a second solvent, and wherethe first solvent and the second solvent are orthogonal solvents; andforming a first electrical contact and a second electrical contact(source and drain) on the semiconductor layer, thereby providing atop-contact bottom-gate organic field effect transistor. The method caninclude curing the dielectric layer, for example, by heating, byradiation, or by both heating and radiation (in either order) to inducecrosslinking.

In some embodiments, the method can include depositing a dielectriccomposition according to the present teachings onto a substrate (gate)to form a dielectric layer, wherein the dielectric composition includesone or more linear polymers described herein dissolved in a firstsolvent; forming a first electrical contact and a second electricalcontact (source and drain) above the dielectric material; and depositinga semiconducting composition above the first and second electricalcontacts and the dielectric layer (i.e., to cover the electricalcontacts and an area of the dielectric material between the electricalcontacts) to form a semiconductor layer, where the semiconductingcomposition includes one or more semiconducting compounds (e.g., smallmolecule compounds or polymers) dissolved in a second solvent, and wherethe first solvent and the second solvent are orthogonal solvents; toprovide a bottom-contact bottom-gate organic field effect transistor.The method can include curing the dielectric layer, for example, byheating, by radiation, or by both heating and radiation (in eitherorder) to induce crosslinking.

In some embodiments, the method can include forming a first electricalcontact and a second electrical contact (source and drain) on asubstrate; depositing a semiconducting composition above the first andsecond electrical contacts (i.e., to cover the electrical contacts andan area of the substrate between the electrical contacts) to form asemiconductor layer, where the semiconducting composition includes oneor more semiconducting compounds (e.g., small molecule compounds orpolymers) dissolved in a first solvent; depositing a dielectriccomposition according to the present teachings above the semiconductorlayer to form a dielectric layer, where the dielectric compositionincludes one or more linear polymers described herein dissolved in asecond solvent, and where the first solvent and the second solvent areorthogonal solvents; and forming a third electrical contact (gate) abovethe dielectric material, wherein the third electrical contact is abovean area between the first and second electrical contacts, to provide abottom-contact top-gate organic field effect transistor. The method caninclude curing the dielectric layer, for example, by heating, byradiation, or by both heating and radiation (in either order) to inducecrosslinking.

In some embodiments, the method can include depositing a semiconductingcomposition on a substrate to form a semiconductor layer, where thesemiconducting composition includes one or more semiconducting compounds(e.g., small molecule compounds or polymers) dissolved in a firstsolvent; forming a first electrical contact and a second electricalcontact (source and drain) above the semiconductor layer; depositing adielectric composition according to the present teachings above thefirst and second electrical contacts and an area of the semiconductorlayer between the first and second electrical contacts to form adielectric layer, where the dielectric composition includes one or morelinear polymers described herein dissolved in a second solvent, andwhere the first solvent and the second solvent are orthogonal solvents;and forming a third electrical contact (gate) above the dielectricmaterial, wherein the third electrical contact is above an area betweenthe first and second electrical contacts, to provide a top-contacttop-gate organic field effect transistor. The method can include curingthe dielectric layer, for example, by heating, by radiation, or by bothheating and radiation (in either order) to induce crosslinking.

In some embodiments, the method can include depositing a dielectriccomposition according to the present teachings onto a substrate (gate)to form a dielectric layer, wherein the dielectric composition includesone or more linear polymers described herein; forming a metal oxidesemiconductor layer on the dielectric layer; and forming a firstelectrical contact and a second electrical contact (source and drain) onthe semiconductor layer, thereby providing a top-contact bottom-gatemetal oxide field effect transistor. The method can include curing thedielectric layer, for example, by heating, by radiation, or by bothheating and radiation (in either order) to induce crosslinking.

In some embodiments, the method can include depositing a dielectriccomposition according to the present teachings onto a substrate (gate)to form a dielectric layer, wherein the dielectric composition includesone or more linear polymers described herein; forming a first electricalcontact and a second electrical contact (source and drain) above thedielectric material; and forming a metal oxide semiconductor layer abovethe first and second electrical contacts and the dielectric layer (i.e.,to cover the electrical contacts and an area of the dielectric materialbetween the electrical contacts), to provide a bottom-contactbottom-gate metal oxide field effect transistor. The method can includecuring the dielectric layer, for example, by heating, by radiation, orby both heating and radiation (in either order) to induce crosslinking.

In some embodiments, the method can include forming a first electricalcontact and a second electrical contact (source and drain) on asubstrate; forming a metal oxide semiconductor layer above the first andsecond electrical contacts (i.e., to cover the electrical contacts andan area of the substrate between the electrical contacts); depositing adielectric composition according to the present teachings above thesemiconductor layer to form a dielectric layer, where the dielectriccomposition includes one or more linear polymers described herein; andforming a third electrical contact (gate) above the dielectric material,wherein the third electrical contact is above an area between the firstand second electrical contacts, to provide a bottom-contact top-gatemetal oxide field effect transistor. The method can include curing thedielectric layer, for example, by heating, by radiation, or by bothheating and radiation (in either order) to induce crosslinking.

In some embodiments, the method can include forming a metal oxidesemiconductor layer on a substrate; forming a first electrical contactand a second electrical contact (source and drain) above thesemiconductor layer; depositing a dielectric composition according tothe present teachings above the first and second electrical contacts andan area of the semiconductor layer between the first and secondelectrical contacts to form a dielectric layer, where the dielectriccomposition includes one or more linear polymers described herein; andforming a third electrical contact (gate) above the dielectric material,wherein the third electrical contact is above an area between the firstand second electrical contacts, to provide a top-contact top-gate metaloxide field effect transistor. The method can include curing thedielectric layer, for example, by heating, by radiation, or by bothheating and radiation (in either order) to induce crosslinking.

The semiconductor layer and the various electrical contacts can beformed by various deposition processes known to those skilled in theart. For example, the semiconductor layer can be formed by processessuch as, but not limited to, sputtering, ion-assisted deposition (IAD),physical vapor deposition, different types of printing techniques (e.g.,flexo printing, litho printing, gravure printing, ink-jetting, padprinting, and so forth), drop casting, dip coating, doctor blading, rollcoating, and spin-coating. In preferred embodiments, the semiconductorlayer is formed from a solution-phase process such as spin-coating, slotcoating, or printing. Electrical contacts can be formed by processessuch as, but not limited to, thermal evaporation and radiofrequency ore-beam sputtering, as well as various deposition processes, includingbut not limited to those described immediately above (e.g., flexoprinting, litho printing, gravure printing, ink-jetting, pad printing,screen printing, drop casting, dip coating, doctor blading, rollcoating, and spin-coating).

Yet another aspect of the present teachings relates to methods forfabricating field effect transistors that include a surface-modifyinglayer of the present teachings. For example, the method can includedepositing a surface modifier composition onto a substrate (e.g.,glass), wherein the surface modifier composition includes one or morelinear polymers described herein, prior to formation of the source anddrain contacts, formation of the semiconductor layer, formation of thegate dielectric layer, and formation of the gate contact (regardless ofsequence of these steps as required by the desired configuration). Themethod can include curing the surface-modifying layer, for example, byheating, by radiation, or by both heating and radiation (in eitherorder) to induce crosslinking.

A further aspect of the present teachings relates to methods forfabricating field effect transistors that include an encapsulation layerof the present teachings. For example, subsequent to the formation ofthe TFT stack, the method can include depositing a composition includingone or more linear polymers of the present teachings over the entire TFTstack to form an encapsulation layer, and optionally curing theencapsulation layer by heating, by radiation, or by both heating andradiation (in either order) to induce crosslinking.

The following examples are provided to illustrate further and tofacilitate the understanding of the present teachings and are not in anyway intended to limit the invention.

Example 1: Synthesis of 5-norbornene-2-methyl Cinnamate

To a 50-ml round bottom flask cooled to 0° C. under nitrogen were added5-norbornene-2-methanol (1.5 g, 12.1 mmol), trimethylamine (8.4 ml, 61mmol), N,N-dimethyl-4-aminopyridine (37 mg, 0.3 mmol) anddichloromethane (2 ml). Then a solution of cinnamoyl chloride (2.22 g,13.3 mmol) in dichloromethane (6 ml) was added dropwise to the reactionmixture. After 10 minutes, it was warmed to the room temperature andstirred overnight. The reaction solution was diluted by dichloromethane(14 ml) and washed by saturated sodium bicarbonate solution andsaturated ammonium chloride, successively. The organic phase wasseparated, dried over sodium sulfate, filtered, concentrated andpurified by column chromatography with hexane to ethyl acetate 20:1 asthe eluent. After concentration, a colorless oil was obtained (2.5 g,yield 81%). ¹H NMR (CDCl₃, 400 MHz): δ=7.72-7.62 (m, 1H), 7.57-7.48 (m,2H), 7.42-7.30 (m, 3H), 6.50-6.39 (m, 1H), 6.20-5.95 (m, 2H), 4.32-3.72(m, 2H), 2.94-2.75 (m, 2H), 2.51-2.40 (m, 1H), 1.93-1.75 (m, 1H),1.49-1.14 (m, 2H), 0.98-0.53 (m, 1H).

Example 2: Synthesis of Poly(5-norbornene-2-methyl Cinnamate) byRing-Opening Metathesis Polymerization

Method A. To a 200-mL round bottom flask under nitrogen, 0.5 g of5-norbornene-2-methyl cinnamate and 50 mL of anhydrous methylenechloride were added. The mixture was kept stirring at r.t. for 30 min toform homogeneous solution. Then Grubbs catalyst (2^(nd) Generation)solution (21 mg in 2 mL anhydrous methylene chloride) was added. Thereaction mixture was kept stirring at r.t. for 12 h. The polymerizationwas quenched by adding 2 mL of ethyl vinyl ether and stirring at r.t.for 1 h. The methylene chloride solution was added dropwise into 250 mLof methanol. The white precipitate was collected by filtration,re-dissolved into 50 mL of methylene chloride, and added dropwise into250 mL of methanol. The final white precipitate was collected byfiltration, washed by 100 mL of methanol, and dried under vacuum at r.t.overnight. Yield 30%. M_(n) 294 k with PDI 1.87 from GPC. ¹H NMR (CDCl₃,400 MHz): δ=7.70-7.52 (broad, m, 1H), 7.52-7.40 (broad, s, 2H),7.38-7.25 (broad, s, 3H), 6.45-6.30 (broad, m, 1H), 5.45-5.05 (broad, m,2H), 4.25-3.87 (broad, m, 2H), 2.10-1.75 (broad, s, 2H), 3.15-2.15(broad, m, 3H), 1.35-1.05 (broad, s, 2H).

Method B. To a 200-mL round bottom flask under nitrogen, a solution ofGrubbs catalyst (2^(nd) Generation) (5 mg in 25 mL of anhydrousmethylene chloride) was added. Then 0.5 g of 5-norbornene-2-methylcinnamate in 25 mL of anhydrous methylene chloride solution was addeddropwise to the reactor within 1 h. The reaction mixture was keptstirring at r.t. for 12 h. The polymerization was quenched by adding 2mL of ethyl vinyl ether and stirring at r.t. for 1 h. The methylenechloride solution was added dropwise into 250 mL of methanol. The whiteprecipitate was collected by filtration, re-dissolved into 50 mL ofmethylene chloride, and added dropwise into 250 mL of methanol. Thefinal white precipitate was collected by filtration, washed by 100 mL ofmethanol, and dried under vacuum at r.t. overnight. Yield 72%. M_(n) 354k with PDI 1.96 from GPC. ¹H NMR (CDCl₃, 400 MHz): δ=7.70-7.52 (broad,m, 1H), 7.52-7.40 (broad, s, 2H), 7.38-7.25 (broad, s, 3H), 6.45-6.30(broad, m, 1H), 5.45-5.05 (broad, m, 2H), 4.25-3.87 (broad, m, 2H),2.10-1.75 (broad, s, 2H), 3.15-2.15 (broad, m, 3H), 1.35-1.05 (broad, s,2H).

Example 3: Top-Gate Bottom-Contact OTFT Devices withPoly(5-norbornene-2-methyl Cinnamate) as the Dielectric Layer

Top-gate bottom-contact OTFTs were fabricated on glass substrates.Substrates were cleaned with soap, DI water, acetone and 2-propanol inan ultrasonic bath for 15 minutes each. A polymeric buffer layer (200nm) was spin-coated onto the substrates, crosslinked by flood UVirradiation (1090 mJ) and baked at 110° C. for 5 minutes. A 50 nm Aglayer was evaporated under high vacuum (5×10⁻⁶ Torr) through a shadowmask to create source and drain electrodes. The fabricated devices havea channel length and width of 60 μm and 1000 μm, respectively. Prior toOSC deposition, a sulfide derivative (2% vol in anisole) was grafted onthe electrodes to modify the silver work function. A PDICN₂-basedsemiconductor layer (30 nm) was deposited by spin-coating. The OSC layerwas annealed for 5 minutes at 110° C. to remove solvent residues. Apolymeric interfacial layer of ˜60 nm thickness was deposited onto theOSC by spin-coating followed by baking at 110° C. for 5 minutes. An 80mg/ml solution of poly(5-norbornene-2-methyl cinnamate) incyclopentanone with 2 wt % of 1-chloro-4-propoxythioxanthone was thenspin-coated on top of the interfacial layer, crosslinked under flood UV(1090 mJ) and baked at 110° C. for 10 minutes to serve as a dielectriclayer of ˜800 nm thickness. Devices were completed by thermallyevaporating a 50-nm thick silver gate electrode. Devices were measuredin ambient atmosphere using a Keithley 4200 parameter analyzer. Thetypical transfer characteristic for devices is given in FIG. 3.Electrical parameters extracted for I_(d)-V_(g) characteristics aregiven in Table 1.

TABLE 1 Mobility polymer I_(d)-V_(g) plot (cm²/Vs) V_(on) (V)poly(5-norbornene-2-methyl FIG. 3 3.98E−1 −2.5 cinnamate)

Example 4: Synthesis of Poly(norbornene-co-norbornene Methanol) andPoly(norbornene-co-norbornene Anhydride) by Ring-Opening MetathesisPolymerization

Poly(norbornene-co-norbornene methanol) was prepared as follows: To a500-mL round bottom flask under nitrogen, 2 g of norbornene, 0.26 g ofnorbornene methanol, and 200 mL of anhydrous methylene chloride wereadded. The mixture was kept stirring at r.t. for 30 min. Then a solutionof Grubbs catalyst (2^(nd) generation) (2.1 mg in 2 mL of anhydrousmethylene chloride) was added. The reaction mixture was kept stirring atr.t. for 12 h. The polymerization was quenched by adding 2 mL of ethylvinyl ether and stirring at r.t. for 1 h. The methylene chloridesolution was added dropwise into 600 mL of methanol. The whiteprecipitate was collected by filtration, re-dissolved into 100 mL ofmethylene chloride, and added dropwise into 600 mL of methanol. Thefinal white precipitate was collected by filtration, washed by 300 mL ofmethanol, and dried under vacuum at r.t. overnight. Yield: 2.1 g (93%).M_(n) 853 K with PDI 1.42 from GPC.

A copolymer of norbornene and 5-norbornene-2-methyl cinnamate(Example 1) can be synthesized analogously.

Poly(norbornene-co-norbornene anhydride was synthesized using analogousprocedures described in this example. Yield: 2.65 g (75%). M_(n) 488 Kwith PDI 1.61 from GPC.

All publications, patent applications, patents, and other referencesmentioned herein are incorporated by reference in their entirety. Incase of conflict, the present specification, including definitions,controls.

The invention claimed is:
 1. An electronic device comprising atransistor component having a semiconductor layer comprising asemiconducting electronic material, a dielectric layer comprising aninsulating electronic material, and source, drain, and gate electrodeseach comprising a conducting electronic material, wherein the transistorcomponent comprises: an organic material comprising a linear polymerhaving a repeating unit of formula (A):

wherein: X and Y independently are selected from the group consisting ofCH₂, CHR, CR₂, C(O), SiH₂, SiHR, SiR₂, NH, NR, O, and S, wherein R isselected from the group consisting of a halogen, —OR^(a), —C(O)OR^(a),—OC(O)R^(a), —NR^(b)R^(c), —C(O)NR^(b)R^(c), —OC(O)NR^(b)R^(c), a C₁₋₁₀alkyl group, a C₁₋₁₀ haloalkyl group, and an optionally substituted arylor heteroaryl group, R^(a) is a C₁₋₁₀ alkyl group or a —Si(C₁₋₁₀ alkyl)₃group, and R^(b) and R^(c) independently are H or a C₁₋₁₀ alkyl group;W—Z is CH═CH or

R¹, R², R³, and R⁴ independently are selected from the group consistingof H, —OR^(d), —C(O)OR^(d), —OC(O)OR^(d), a C₁₋₁₀ alkyl group, a C₁₋₁₀haloalkyl group, and L-Q, wherein L is selected from the groupconsisting of —O—, —C(O), a divalent C₁₋₁₀ alkyl group, a divalent C₆₋₁₈aryl group, a covalent bond, and combinations thereof, Q is acrosslinkable group comprising, a —CH═CH₂ moiety, a —CH═CH—CH₃ moiety, a—CH═C(CH₃)₂ moiety, a —C(CH₃)═CH₂ moiety, an ethynyl moiety, a dienylmoiety, an acrylate moiety, a coumarinyl moiety, an epoxy moiety, or acombination thereof, and R^(d) is H or a C₁₋₁₀ alkyl group, providedthat at least one of R¹, R², R³, and R⁴ is L-Q; and m is 0, 1 or 2;wherein either the dielectric layer comprises the organic material asthe insulating electronic material or the organic material is in contactwith at least one of the semiconducting electronic material, theinsulating electronic material, and the conducting electronic material.2. The electronic device of claim 1, wherein the linear polymercomprises a repeating unit of formula (II):

wherein x is selected from the group consisting of CH₂,CHR, CR₂, C(O),and O; and L-Q is selected from the group consisting of:

wherein R¹ is a H or C₁₋₂₀ alkyl group.
 3. The electronic device ofclaim 2, wherein X is CH₂.
 4. The electronic device of claim 1, whereinthe linear polymer having a repeat unit of formula (A) is derived fromring-opening metathesis polymerization of a monomer selected from thegroup consisting of:

wherein R′ is H or OCH₃; and n is an integer from 1 to
 10. 5. Theelectronic device of claim 1, wherein the linear polymer comprises asecond repeating unit in addition to the repeating unit of formula (A),wherein the second repeating unit is represented by formula (C)

wherein: X′ and Y′ independently are selected from the group consistingof CH₂, CHR, CR₂, C(O), SiH₂, SiHR, SiR₂, NH, NR, O, and S, wherein R isselected from the group consisting of a halogen, —OR^(a), —C(O)OR^(a),—OC(O)R^(a), —NR^(b)R^(c), —C(O)NR^(b)R^(c), —OC(O)NR^(b)R^(c), a C₁₋₁₀alkyl group, a C₁₋₁₀ haloalkyl group, and an optionally substituted arylor heteroaryl group, R^(a) is a C₁₋₁₀ alkyl group or a —Si(C₁₋₁₀ alkyl)₃group, and R^(b) and R^(c) independently are H or a C₁₋₁₀ alkyl group;W′—Z′ is CH═CH or

R⁶, R⁷, R⁸, and R⁹ independently are selected from the group consistingof H and -L-T, wherein L′ is selected from the group consisting of —O—,—C(O)—, a divalent C₁₋₁₀ alkyl group, a divalent C₆₋₁₈ aryl group, acovalent bond, and combinations thereof; and T is H, OH, a C₁₋₁₀ alkylgroup, a C₁₋₁₀ haloalkyl group, a C₁₋₁₀ alkoxy group, an OC(O)(C₁₋₁₀alkyl) group, a —Si(OC₁₋₁₀ alkyl)₃ group, and a phenyl group optionallysubstituted with 1-5 groups independently selected from halo, OH, aC₁₋₁₀ alkyl group, a C₁₋₁₀ haloalkyl group, and a C₁₋₁₀ alkoxy group;and m′ is 0, 1 or
 2. 6. The electronic device of claim 1, wherein thelinear polymer comprises a second repeating unit in addition to therepeating unit of formula (A), wherein the second repeating unit isrepresented by


7. The electronic device of claim 1, wherein the linear polymercomprises a second repeating unit in addition to the repeating unit offormula (A), wherein the second repeating unit is represented by

wherein R⁵ is selected from the group consisting of H, L′-T, and L′-Q,wherein L is selected from the group consisting of —O—, —C(O)—, adivalent C₁₋₁₀ alkyl group, a divalent C₆₋₁₈ aryl group, a covalentbond, and combinations thereof; L′ is selected from the group consistingof —O—, —C(O)—, a divalent C₁₋₁₀ alkyl group, a divalent C₆₋₁₈ arylgroup, a covalent bond, and combinations thereof; Q is a crosslinkablegroup comprising an ethenyl moiety, an ethynyl moiety, a dienyl moiety,an acrylate moiety, a coumarinyl moiety, an epoxy moiety, or acombination thereof; and T is H, OH, a C₁₋₁₀ alkyl group, a C₁₋₁₀haloalkyl group, a C₁₋₁₀ alkoxy group, an OC(O)(C₁₋₁₀ alkyl) group, a—Si(OC₁₋₁₀ alkyl)₃ group, and a phenyl group optionally substituted with1-5 groups independently selected from halo, OH, a C₁₋₁₀ alkyl group, aC₁₋₁₀ haloalkyl group, and a C₁₋₁₀ alkoxy group.
 8. The electronicdevice of claim 1, wherein the linear polymer is partially hydrogenated.9. The electronic device of claim 8, wherein the linear polymer ispartially hydrogenated such that no more than about 50% of theunsaturated bonds in the backbone of the linear polymer arehydrogenated.
 10. The electronic device of claim 1, wherein the linearpolymer is end-functionalized with a photocrosslinkable moiety selectedfrom the group consisting of an acrylate group and a cinnamate group.11. The electronic device of claim 1, wherein the organic materialcomprises a crosslinked matrix of the linear polymer.
 12. The electronicdevice of claim 1, wherein the organic material comprising the linearpolymer having a repeating unit of formula (A) is present in an organiclayer coupled to the semiconductor layer, the gate electrode, or thesource and drain electrodes, the organic layer functioning as apassivation layer or a surface-modifying layer.
 13. The electronicdevice of claim 1, wherein the organic material comprising the linearpolymer having the repeating unit of formula (A) is present as anadditive in the semiconductor layer.
 14. The electronic device of claim1, wherein the field-effect transistor comprises a dielectric layercoupled to the semiconductor layer on one side and the gate electrode onanother side, wherein the dielectric layer comprises the organicmaterial comprising the linear polymer having a repeating unit offormula (A).
 15. The electronic device of claim 14, wherein thedielectric layer is in the form of a multi-layer laminate, and whereinat least one layer of the multi-layer laminate comprises the organicmaterial comprising the linear polymer having a repeating unit offormula (A).
 16. The electronic device of claim 15, wherein themulti-layer laminate comprises at least one layer comprising a lineardielectric polymer that is different from the linear polymer having arepeating unit of formula (A).
 17. The electronic device of claim 14,wherein the dielectric layer comprises a crosslinked matrix of thelinear polymer having a repeating unit of formula (A).
 18. Theelectronic device of claim 14, wherein the semiconductor layer comprisesan organic semiconducting material.
 19. The electronic device of claim14, wherein the semiconductor layer comprises a metal oxidesemiconducting electronic material.
 20. The electronic device of claim19, wherein the metal oxide semiconducting electronic material comprisesindium-gallium-zinc oxide.
 21. The electronic device of claim 1, whereinQ is an epoxy moiety.
 22. The electronic device of claim 1, wherein X isCH₂ and m is 0.